CN109399856A - A kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation - Google Patents

A kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation Download PDF

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Publication number
CN109399856A
CN109399856A CN201710711257.1A CN201710711257A CN109399856A CN 109399856 A CN109399856 A CN 109399856A CN 201710711257 A CN201710711257 A CN 201710711257A CN 109399856 A CN109399856 A CN 109399856A
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semi
ozone
water
coke wastewater
discharge treatment
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于永辉
王维
李先如
卫皇曌
孙承林
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The present invention is a kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation, mainly includes the units such as sloping plate deposition, multiphase air bearing, multi-medium filtering, ammonia still process, catalytic ozonation, preaeration, multi-stage biological processing, residual ozone oxidation and film process.The invention belongs to Treatment of Coking Effluent fields, the zero discharge treatment especially suitable for semi-coke wastewater.The processing method of semi-coke wastewater is main are as follows: semi-coke wastewater first passes around sloping plate deposition and air flotation cell, using multi-medium filtering unit, the oil in waste water is largely removed with suspended matter at this time, ammonia still is passed through in water outlet, waste water enters device for catalyzing and oxidating ozone after ammonia still process, waste water after treated by ozone is respectively used to supplement the recirculated water of cooling washing coal gas, quenching and entrance multi-stage biological aoxidize, waste water flows into residual ozone oxidizing tower after biological treatment, water outlet enters film process unit in tower, film water outlet can be used for other different demands water in factory, water resource is effectively saved.

Description

A kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation
Technical field
The invention belongs to Technologies of Coke Plant Wastewater Treatment field, suitable for coking, the place of semicoke high-concentration organic industrial waste water Reason.
Background technique
Water resources in china occupancy volume per person occupies the 108th, the world, is one of 21 poor-waters and the country of most water shortage in the world, Fresh water occupancy volume is only 1/4 of the world per capita per capita.With population growth, Regional Economic Development, industrialization and urbanization process Accelerate, municipal water demand constantly increases, will make water resource it is insufficient, with water shortage problem, necessarily become and restrict economic society The main resistance and obstacle that can develop.
The enterprises such as coking, semicoke are generally seated the more rich area of coal resources, and the general water resource in these areas is short It lacks.Semi-coke is the product of low temperature distillation in coal, and the waste water in production process is mainly derived from the recirculated water of washing coal gas, water quality General COD high, ammonia nitrogen be high, color depth, phenol and ammonia taste is big and biodegradability poor (Tan Xiaoting, Zheng Huaan etc., at semi-coke wastewater It manages status and preconditioning technique is in progress, Treatment of Industrial Water, 2014；Luo Xiongwei, horse bezoar qi, coal semi-coke wastewater processing technique into Exhibition, Coal dressing and comprehensive utilization.2015).As Environmental Protection in China regulation is increasingly stringenter and the formal promulgation of " ten, water ", The processing of semi-coke wastewater faces more acute challenge.The zero discharge treatment of semi-coke wastewater for coal chemical enterprise be one well Selection, that is, saved water resource, while solving the problems, such as not up to standard to discharge again.Catalytic ozonation technology has operation The advantage easy, decoloring ability is strong, without secondary pollution cooperates researched and developed ozone catalyst that oxidation effectiveness and energy can be improved Biodegradability is substantially improved, reduces subsequent biological treatment difficulty.
Summary of the invention
The present invention is a kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation.
The present invention is characterized in that:
A kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation includes sloping plate deposition, multiphase air bearing, more Media filtration, ammonia still process, catalytic ozonation, preaeration, multi-stage biological processing, residual ozone Air Exposure process.
The filtrate of multi-medium filtering is several combinations of coke, active carbon, quartz sand, walnut shell, using the production of production Product and achieve the purpose that reduce operating cost.
Wastewater pH is adjusted between 11~12 with the concentrated sulfuric acid when ammonia still process, and steaming ammonium hydroxide volume is 3%~5%, and ammonia nitrogen is gone Except rate is 70.5%~85.2%, it is discharged pH8~10.
Multi-stage biological processing uses anoxic, anaerobism, aerobic thtee-stage shiplock, and anoxic biological treatment front end is equipped with preaeration, mesh Be to remove the ozone that dissolves in waste water；Starting excess sludge of the sludge from coal chemical industry sewage treatment plant of biological treatment.
Filling our factory's semicoke product plays the role of mass transfer enhancement and absorption in residual ozone oxidizing tower, and residual ozone can have Effect kills bacterium, and there are also certain decolorizations, improves ozone comprehensive utilization ratio.
Film process unit mainly includes micro-filtration, ultrafiltration and reverse osmosis, different is required with water purposes, it can be achieved that wherein to meet Certain a kind of exclusive use of membrane module and being used in series for inhomogeneity membrane module, can also reduce operating cost in this way.
It is a% active carbon+b% Aluminum sol+c% silica solution that ozone catalytic oxidation catalyst carrier, which forms (mass fraction), Wherein a=50~80, b=10~30, c=5~20；Active component (mass fraction) is x%Fe+y%Mn+z% in catalyst Ce, wherein x=0.5~3, y=0.5~3, z=0.5~2；Catalyst loading is the 0.5~1.5 of wastewater volume amount per hour Times.
Compared with the conventional method, this method realizes zero-emission after semi-coke wastewater processing, and water resource is recycled.Ozone Catalysis oxidation can reduce COD and ammonia nitrogen simultaneously, have preferable removal effect to phenolic substances, improve wastewater biodegradability, reduce Influence of the phenolic substances to subsequent biological treatment.This method also achieves ozone secondary use, improves ozone comprehensive utilization ratio, and two It is secondary it is ozonation aerated can effectively kill bacterium, avoid microbial reproduction from leading to the blocking of film unit below.
Detailed description of the invention
The COD removal rate comparison diagram of the independent ozone of Fig. 1 and catalytic ozonation.
A kind of semi-coke wastewater Zero-discharge treating process schematic diagram based on catalytic ozonation of Fig. 2.
Specific embodiment
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
1, semi-coke wastewater initially enters sloping plate deposition district, and inclined plate tilt angle is 30 degree, partial suspended thing in water and again Oil is removed herein, enters air flotation cell later, flotation tank is flat flow, length-width ratio 3:1, reflux ratio 25%, dissolving Operating pressure is 0.4MPa, and for air demand by volume of the 8% of inflow, the micro-bubble that air floatation machine generates can will be in waste water Fine suspension and light oil take the water surface to and remove, and when waste water enters multi-medium filtering tower, remaining suspended matter and oil are cut It stays and adsorbs, wherein the first filtering inner-tower filling material is partial size d10For the quartz sand of 1.0mm, the second filtering inner-tower filling material is partial size d10For each half of quartz sand and walnut shell of 0.8mm, it is partial size d that third, which filters inner-tower filling material,10For the coke of 0.5mm, filtration tank Filtering velocity is 8m/h, backwashing period 12h, first with 17L/ (m2S) intensity gas backwashes 3min, after with 10L/ (m2·s) Intensity water backwashing 5min；
2, the multi-medium filtering water outlet concentrated sulfuric acid enters ammonia still after adjusting pH to 11~12, after steaming 3%~5% waste water Ammonia nitrogen is largely distilled out of, and remaining waste water enters catalytic ozonation tower, is discharged lighter, and phenol organic matter is oxidized, phenol Taste and ammonia taste disappear, and biodegradability improves, and water outlet a part is used for quenching, and a part is for supplementing the circulation of cooling washing coal gas Water, remaining water enter preaeration unit, have not only achieved the purpose that water resource recycles, but also reduce accounting for for subsequent biological treatment facility Ground area；
Embodiment 1
10m3/ h semi-coke wastewater continuously enters inclined-plate clarifying basin, in settling zone residence time 20min, passes in and out water quality such as table 1.
The water quality of 1 raw water of table and precipitating water outlet
Analysis project SS(mg/L) Petroleum-type (mg/L)
Raw water 1570 363
After sloping plate deposition 526 215
Embodiment 2
Inclined-plate clarifying basin water outlet enters pressurized dissolved air flotation equipment, stops 12min in flotation tank, takes the water outlet from overflow port Analyze result such as table 2.
2 air bearing effluent quality of table
Analysis project SS(mg/L) Petroleum-type (mg/L)
After air bearing 88 39
Embodiment 3
Flotation tank water outlet enters multi-medium filtering tower, and after three-stage filtration, the surplus of oil and suspended matter reaches in waste water To the requirement for entering next processing unit, result such as table 3.
Table 3 filters effluent quality
Analysis project SS(mg/L) Petroleum-type (mg/L)
After filtering 12 5
Embodiment 4
Semi-coke wastewater is adjusted between pH=11~12 after filtering, steams ammonium hydroxide 3% by packed tower, sampling analysis compares steaming Remaining waste water and raw water difference such as table 4.
The water quality of water after 4 raw water of table and ammonia still process
Analysis project COD(mg/L) Ammonia nitrogen (mg/L) pH
Raw water 33410 3882 9.1
After ammonia still process 28890 1145.5 9.8
Embodiment 5
Catalyst in catalytic ozonation tower is 15 tons of (carriers of catalyst that semi-coke wastewater is impregnated overnight after ammonia still process Group becomes 60wt.% active carbon+20wt.% Aluminum sol+20wt.% silica solution；Active component is 1wt.%Fe+ in catalyst 1wt.%Mn+1wt.%Ce), adjust ozone amount be 50kg/h, the residence time be set to 23min, 30min, 45min, 60min, successive reaction take out water and survey COD and ammonia nitrogen, as a result such as table 5.
The different residence time ozone oxidation effects of table 5
Residence time 60min 45min 30min 23min
COD(mg/L) 7485 10160 12340 26030
Ammonia nitrogen (mg/L) 216.6 278.2 363.6 653.2
As known from Table 5, when ozone flow 50kg/h, residence time 60min, COD and ammonia nitrogen removal frank respectively reach 74% With 81%, pH=8.5, it is discharged the tasteless recirculated water that can be used for quenching and the cooling washing coal gas of supplement.
3, the preaeration tank depth of water is not higher than 1m, aeration intensity 3m3/(m2H), there are two purposes for preaeration, first is that passing through Aeration takes away ozone remaining in water body, it is avoided to have an impact microorganism below, second is that oxygen is provided for water body, after satisfaction Continuous biological treatment demand；
Embodiment 6
By semi-coke water sample after the ammonia still process of ozonation aerated processing 1 hour with air aeration 1 hour, sufficiently drive away remaining smelly in water Oxygen investigates the biodegradability of semi-coke wastewater after ozone Oxidation Treatment, measurement result such as table 6.
6 raw water of table and ozone water outlet compare
Project COD(mg/L) BOD(mg/L) Volatile phenol (mg/L) B/C
Raw water 33410 520 4371 0.016
Water after ozone oxidation 7485 3100 2.0 0.414
As known from Table 6, raw water biodegradability is very poor, and semi-coke wastewater B/C > 0.3 after ozone Oxidation Treatment, illustrates through ozone Air Exposure can greatly improve the biodegradability of semi-coke wastewater, be conducive to subsequent biological treatment, this practical process.
4, preaeration water outlet enters multi-stage biological and aoxidizes, and biological oxidation can be biofilm, and filler is not less than effective in pond The half of the depth of water, the microbe-derived residue in sewage treatment plant, Dalian special steel Co., Ltd, northeast special steel group in pond Sludge, waste water initially enter anoxic oxidation pond, and the residence time is 6~16h, enter back into anaerobic oxidation pond, and the residence time is 4~ 12h, finally enters aerobic oxidation pond, and the residence time is 8~for 24 hours, the COD and ammonia nitrogen of water outlet are further decreased, and are substantially met It is subsequent to be required with water；
Embodiment 7
Preaeration water outlet enters three-level biofilm system, initially enters anoxic pond and stops 10h, enters back into anaerobic pond stop 6h finally enters aerobic tank and stops 20h, is discharged result such as table 7.
The biodegradability of 7 raw water of table and ozone water outlet
Project COD(mg/L) NH3-N(mg/L) Volatile phenol (mg/L)
After biological treatment 80 20 0.1
5, biology water outlet enters the residual ozone oxidizing tower of filling semicoke, and residual ozone is made full use of to improve ozone entirety Utilization rate reduces water body chroma, kills the microorganisms such as bacterium in water, while semicoke has suction-operated.
6, the water outlet of residual ozone oxidizing tower is alternative enters film process unit, and film process unit mainly includes micro-filtration, surpasses It filters and reverse osmosis, and can realize wherein certain a kind of exclusive use of membrane module and being used in series for inhomogeneity membrane module, to meet The different requirements for using water purpose in factory.
Embodiment 8
Semi-coke wastewater is most afterwards through tubular type polypropylene (PP) microfiltration membranes, tubular type polysulfones (PS) ultrafiltration membrane and tubular type UTC-70 fragrance After polyamide composite reverse osmosis membrane processing, analysis effluent quality complies fully with the relevant criterion of Treated sewage reusing.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (7)

1. a kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation, it is characterised in that: semi-coke wastewater successively passes through Sloping plate deposition unit, multiphase air flotation cell, multi-medium filtering unit, ammonia still process unit, ozone catalytic oxidation unit, preaeration list It may be recovered utilization after member, multi-stage biological processing unit, residual ozone oxidation unit and film process cell processing.
2. a kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation according to claim 1, feature Be: sloping plate deposition unit is inclined-plate clarifying basin, and multiphase air flotation cell is multiphase flotation tank, and the filtrate of multi-medium filtering is coke One of charcoal, active carbon, quartz sand, walnut shell or two kinds of combination of the above.
3. a kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation according to claim 1, feature It is: adjusts wastewater pH between 11~12 with the concentrated sulfuric acid when ammonia still process, steaming ammonium hydroxide volume is raw wastewater volume 3%~5%, Ammonia nitrogen removal frank is 70.5%~85.2%, is discharged pH=9~10.
4. a kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation according to claim 1, feature It is, multi-stage biological processing is sequentially connected in series using anoxic, anaerobism, aerobic three-level, and anoxic biological treatment front end is equipped with preaeration, mesh Be to remove remaining ozone in waste water.
5. a kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation according to claim 1, feature It is, residual ozone is oxidized to the effect that secondary use ozone primarily serves sterilization, and there are also certain decolorizations, improves ozone Utilization rate.
6. a kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation according to claim 1, feature It is, film process unit mainly includes micro-filtration, ultrafiltration and one of reverse osmosis or two kinds or more, and can realize that wherein certain is a kind of The exclusive use of membrane module and being used in series for inhomogeneity membrane module, to meet the different requirements with water purpose.
7. a kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation according to claim 1, feature It is, the ozone catalytic oxidation catalyst carrier of the ozone catalytic oxidation unit and residual ozone oxidation unit forms (quality Score) it is a% active carbon+b% Aluminum sol+c% silica solution, wherein a=50~80, b=10~30, c=10~20；Catalyst Middle active component (mass fraction) is x%Fe+y%Mn+z%Ce, wherein load capacity x=0.5~3, y=0.5~3, z=0.5 ~2；Catalyst loading is 0.5~1.5 times of wastewater volume amount per hour；The dosage of ozone is waste water per hour per cubic meter 1~15 kilogram.
CN201710711257.1A 2017-08-18 2017-08-18 A kind of semi-coke wastewater Zero discharge treatment method based on catalytic ozonation Pending CN109399856A (en)

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CN111517561A (en) * 2020-03-31 2020-08-11 临涣焦化股份有限公司 Coking chemical product refining wastewater treatment method
CN112777806A (en) * 2021-01-22 2021-05-11 青岛宏仓科技有限公司 Gas-making circulating water treatment device and method
CN115626747A (en) * 2022-11-18 2023-01-20 北京科净源科技股份有限公司 System and method for deeply treating leather wastewater

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111517561A (en) * 2020-03-31 2020-08-11 临涣焦化股份有限公司 Coking chemical product refining wastewater treatment method
CN112777806A (en) * 2021-01-22 2021-05-11 青岛宏仓科技有限公司 Gas-making circulating water treatment device and method
CN115626747A (en) * 2022-11-18 2023-01-20 北京科净源科技股份有限公司 System and method for deeply treating leather wastewater

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